Carboxyl rich alkyd resin-ethoxyline resin compositions and process for their preparation



United States Patent CARBOXYL RICH ALKYD RESIN-ETHOXYLINE RESINCOMPOSITIONS AND PROCESS FOR THEIR PREPARATION Joseph Rosenberg,Schenectady, N.Y., assignor to General Electric Company, a corporationof New York No Drawing. Application August 25, 1954 Serial No. 452,221

Claims. (Cl. 260-22) My invention relates to new and useful resincompositions. More particularly, the invention relates to resincompositions having improved desirable physical and electricalcharacteristics.

Resins of the alkyd type are well-known as being the reaction productsof polyhydric alcohols and polybasic or polycarboxylic acids. Epoxy orethoxyline or epoxide resins are also known in the art. For example, US.Patent 2,324,483, Castan, discloses epoxy resins comprising the reactionproduct of phenols having at least two phenolic hydroxy groups and anepihalogenohydrin, e.g.

epichlorhydrin (the product being cured to the substan- 7 have poorflame-retardant properties, exhibit anundesirable. decrease in strengthat elevated temperatures, and have increasingly poor electricalproperties at elevated temperatures. Copending patent application SerialNo. 305,913, filed August 22,1952, now US. Patent 2,744,845,

2,909,495. Patented Oct. 20, 1959 a carboxyl rich alkyd, or onecontaining free carboxyl groups, comprising the reaction product of ahigher saturated or unsaturated fatty acid withhexachloroendomethylenetetrahydrophthalic acid or anhydride, (2) acomplexepoxide resin containing epoxy groups and comprising a polyetherderivative of a polyhydric organic compound, such as a polyhydricalcohol or phenol, and (3) hexachloroendomethylenetetrahydrophthalicanhydride. These resinous compositions are characterized by desirablephysical characteristics at the operating temperatures of electricaldevices.

The features of my invention which I believe to be novel are set forthwith particularity in the appended claims. My invention itself, however,both as to its organization andmethod of operation, together withfurther objects and advantages thereof, may best be understood byreference to the following description.

The ethoxyline resins defined above as utilized in my invention arewell-known in the art. They are described in Castan Patents 2,324,483and 2,444,333, British Patent 518,057, and British Patent 579,698.Generally, the ethoxyline resins described therein are the reactionproduct of an eiphalogenohydrin such as epichlorohydrin and a phenolhaving at least two phenolic hydroxy groups, such as bis-(4-hydroxyphenyl) dimethylmethane. US. Patents 2,494,295; 2,500,600, and 2,511,913also disclose ethoxyline resins which may be used in connection with thepresent invention. The above patents are hereby incorporated byreference into this application. The ethoxyline resins used hereincontain more than one epoxy group per molecule. They may be prepared byreacting a polyhydric alcohol or phenol, such as hydroquinone,resorcinol, glycerin, and condensation products of phenols with ketones,for example, bis-(4-hydroxy phenol) 2,2- propane with epichlorhydrin. Asan example, the reaction of epicblorhydrin withbis-(4-hydroxyphenal)-2,2- propane may be illustrated as follows:

describes the curing of ethoxyline resins in combination withhexachloroendomethylenetetrahydrophthalic anhydride to obtain resinshaving improved hardness and electrical qualities at high temperatures.While these properties, among others, are very useful, there is adefinite need for compositions comprising ethoxyline resins having thedesirable high temperature properties of resins cured withhexachlor'oendomethylenetetrahydrophthalic anhydride which are alsoflexible. For example, ethoxyline resin compositions cured withhexachloroendom'ethylenetetrahydrophthalicanhydride would, because oftheir electrical characteristics and heat resistance, be very useful asstator bar insulation for electrodynamic machinery except that such ause requires a flexible resin. Flexibility and flame resistance are alsorequired, for example, in bus bar insulation for electricalequipment.

' It is, therefore, an object of my invention toprovide resincompositions comprising ethoxyline resin which are heat andflame-resistant and which have suitable electrical characteristics andare flexible.

Briefly stated, my invention comprises combining (1) A where n has anaverage value ranging from about 0 to about 7. Such ethoxyline resinsare sold under the name of Epon resins by Shell Chemical Corporation, orunder the name Araldite by Ciba Company. Pertinent data on Epon resinsare given 1n Table I below:

TABLE I V Approximate Epon No. Epoxide Esterifica- M.P., 0.

Equivalent tion Equivalent 192 9 225-290 20-28 450-425 64-76 905-98597-103 1, 600-1, 900 127-133 2, 400-4, 000 200 145-155 140-165 Liquid300-375 105 40-45 The carboxyl rich alkyd resin of my invention is madeby. reacting hexachloroendomethylenetetrahydrophthalic anhydride or acidwith a monoglyceride of a fatty acid having morethan twelve carbons. Ithasbeen found that monoglycerides of fatty acids having twelve orfewercarbons do not produce flexible materials. Care is taken that thehexachloroendomethylenetetrahydrophthalic acid or anhydride is presentin excess over the amount of flexible and tough at temperatures fromabout 20 C and the like.

monoglyceride used to furnish a carboxyl rich alkyd. Thus, I may employfor each mol of monoglyceride from 0.7 to 1.5 mols and, preferably onemol hexachloroendomethylenetetrahydrophthalic acid or anhydride. Variousmonoglycerides may be used, for example those of ricinoleic acid,tridecylic acid, myristic acid, pentadecylic acid,

palmitic acid, margaric acid, stearic acid, oleic acid, and .the like,the only limitation being that the fatty acid should have at leastthirteen carbons. Hydrogenated monoglycerides, of which the hydrogenatedmonoglyceride f ricinoleic acid is an example, are also useful inconnection with my invention.

It has been found that useful alkyds for the purpose of this inventionhave an acid number of about 18 to 35. Preferably I use such resinshaving an acid number of from about 25 to 35 and, mostpreferably, aboutthirty. Such alkyds are prepared-by heating a mixture ofhexachloroendomethylenetetrahydrophthalic acid or anhydride andmonoglyceride in proper mol or proportions from one to three hours ormore at a temperature of from 150-250 C. It will be realized, of course,that the reaction is of a time-temperature nature and that lowertemperatures require a longer time of reaction while the reaction atflexibility, I prefer to limit the relative parts by weight of thematerial to from about 300 to 650 parts of alkyd, 100 parts ofethoxyline resin, and 4 to 40 parts ofhexachloroendomethylenetetrahydrophthalic anhydride.

Just as the amounts of ingredients in my resinous end product may bevaried, so may the method of combining them. Preferably the alkyd andethoxyline resins are mixed together, and heated to about 150 C. to 170C., and the hexachloroendomethylenetetrahydrophthalic anhydride added tothe mixture and then cured. The time of reaction will vary dependingupon the exact temperature used and upon the type of end productdesired, i.e. liquid which may be stored and later further cured, atacky resinous solid which may be used as is or further cured at a latertime, or a more fully cured resin.

The following examples will serve to illustrate the practice of myinvention so that those skilled in the art may better understand it.

Example 1 An alkyd resin was prepared by heating 186.3 grams (0.5 mol)hexachloroendomethylenetetrahydrophthalie acid and 194.4 grams (0.5 mol)glyceryl monoricinoleate at a temperature of 195 C. for seven andone-half hours. The acid number was 28.5. The alkyd was added in theamount of 33.4 grams to 10 grams of Epon 834 resin and heated withmixing to a temperature of 150 C.Hexachloroendornethylenetetrahydrophthalic anhydride in the amount of3.1 grams was then added to the mix which was cured for three hours at150 C. The product was upward. A strip one-eighth inch thick wasresistant to tearing during the course of wrapping coils, bus bars, The60-cycle power factor at various temperatures was as follows: 25 C.,4.50%; 50 C 6.80%; 75 C., 1.98%; 100 C., 2.10%.

This resin is particularly useful for insulation exposed to hightemperatures and which at such higher temperatures must .have a lowpower factor and other desirable electrical characteristics.

Example 2 Example 1.

was added to 10 grams of Epon 834 resin and heated with mixing to 150 C.Then 1.3 grams of hexachloroendomethylenetetrahydrophthalic anhydridewere added and the mixture cured for three hours at about 150 C. Theproduct was flexible and tough at temperatures from about 20 C. andhigher. The 60-cycle power factors were as follows: 25 C., 8.00%; 50 C.,4.20%; 75 C., 1.13%; C., 5.60%. This resin has the same uses as that ofExample 1.

Example 3 63.1 grams of an alkyd resin prepared as in Example 1 havingan acid number of 30.1 was added to 10 grams of Epon 834 resin andheated with mixing to a temperature of C. When nohexachloroendomethylenetetrahydrophthalic anhydride was added and theresin cured for three hours at 150 C., only a soft mass resulted whichwas not useful for the present purpose. When one gram ofhexachloroendomethylenetetrahydrophthalic anhydride was added to thealkyd-epoxy resin mix before curing, a resin was produced which wasuseful at lower temperatures but which softenedat about 100 C. When 2.0grams of hexachloroendomethylenetetraphthalic anhydride was added beforecuring, the product was flexible and tough at temperatures of about 20C. and higher. The material in sheet form was resistant to tearing andhad a 60-cycle power factor as follows: 25 C., 7.51%; 50 C., 5.33%; 75C., 1.47%; 100 C., 6.20%. This resin is also useful for the samepurposes as that of Example 4 Example 3 was repeated with the exceptionthat 3.0 grams of hexachloroendomethylenetetrahydrophthalic anhydridewere used for curing. The product again was flexible, tear-resistant,and had the following 60-cycle power factor: 25 C., 7.59%; 50 C., 7.36%;75 C., 1.70%; 100 C., 4.81%. This resin has the same uses as the aboveresins.

Example 5 Example 3 was repeated using 4.0 grams ofhexachloroendomethylenetetrahydrophthalic anhydride for the curingstage. The flexible, tear-resistant product which is useful at hightemperatures had a 60-cycle power factor at 25 C., 6.20%; 50 C., 7.79%;75 C., 1.63%; 100 C., 3.26%.

Example 6 experiments carried out that flexible resins having desirableelectrical properties were obtained when with 100 parts by weight ofethoxyline resin the alkyd resin varied from 300 to 650 parts by weight,and the hexachloroendomethylenetetrahydrophthalic anhydride varied fromabout 4 to 40 parts by weight.

Experiments were also carried out to determine the optimum alkyd resinacid number range. It was found that when the acid number fell belowabout 25, the resulting resins tended to have too high a power factorfor high temperature use. With acid numbers above about 35, the resincomposition tended to be too rigid. I'prefer using alkyd resins havingan acid number of about 30 when a flexible resin having good electricalcharacteristics at high temperatures is indicated.

Further experiments were carried out similarly as above but usingphthalic anhydride or acid in lieu ofhexachloroendomethylenetetrahydrophthalic anhydride or acid and in aboutthe same amounts in preparing the alkyd resin component, These resinshad undesirably high 60 cycle power factors ranging from about 4% at 25C. to about 70% at 100 C. Another commercially available flexibleethoxyline resin had a 60 cycle power which ranged from 40% at roomtemperature to almost 100% at 50 C.

Likewise, phthalic anhydride, as typical of the usual curing agents, wasused in lieu of hexachloroendomethylenetetrahydrophthalic' anhydride tocure resins composed of a hexachloroendomethylenetetrahydrophthalicalkyd and ethoxyline resin combination, as in the above examples. It wasfound that the resin had an excessive power factor, especially at thehigher temperatures.

The compositions of my invention are, as pointed out above, very usefulin insulating applications in which the material must be flexible and atthe same time have desirable electrical characteristics at highertemperatures. Of course, either of these properties may be sacrificedvarying other proportions of the alkyd resin, ethoxyline resin, andhexachloroendomethylenetetrahydrophthalic anhydride can be used.

My new materials may also be formed into tape which is flexible,tear-resistant, and very useful for the wrap insulation of apparatussuch as bus bars, coils, and the like. They may also be used as acasting medium for devices such as coils, transformers, and the like. Inthis connection, a sample with embedded electrodes made for testpurposes showed no corona eifect up to about 15 kv., the electrodesbeing spaced one-quarter inch apart. The ability of the resins of myinvention to Withstand temperatures cycling between about 40* C. and 125C. and higher and at the same time having low electrical losses makesthem very efiicacious in many applications, as does their resistance toheat and their flame-retardancy.

My new resinous compositions are also very useful in coating orimpregnating textile or glass, or other types of tape which are to beused for insulating and other purposes. Acetone and other well-knownpolar solvents are used to dissolve the resins. If desired, otherliquids, such as toluene, xylene, benzene, Cellosolve acetate, ethylacetate, and the like may be used in conjunction with the primarysolvent. Varying concentrations of solvent may be used according to thedegree of coating desired and the use of the final product. The materialto be coated or impregnated is passed. through the solution and thendried and cured. These materials are particularly useful where aninsulation which is flexible, has low power factors at high temperaturesand is fire-retardant, is required.

The resinous products of my invention may also be used in preparinglaminated materials, adhesives, and the like. Filler materials ofvarious kinds and characteristics can be added to the resins hereinprovided to make structures or compositions having particular desiredproperties. For example, they may be filled with magnetic powders toprovide magnets. Other fillers include silica, mica, asbestos, titaniumdioxide, clay, carbon graphite, etc. Many other uses for such resinswill occur to those skilled in the art.

While I have described this invention in connection with certainspecific examples, I wish it to be understood that I desire to protectin the following claims all variations of my invention which do notdepart from the spirit or scope thereof.

What I claim as new and desire to secure by Letters Patent of the UnitedStates is:

l. A composition of matter comprising the reaction product of 1) about300 to 650 parts by weight of a carboxyl rich alkyd resin comprising theesterification product of from about 0.7 to 1.5 mols of a materialselected from the class consisting ofhex-achloroendomethyleuetetrahydrophthalic anhydride andhexachloroendomethylenetetrahydrophthalic acid and about one mol of amonoglyceride of a fatty acid having at least 13 carbon atoms, saidalkyd resin having an acid number of from about 18 to 35, (2) about 100parts by weight of a complex epoxide resin containing epoxide groups andcomprising a polyglycidyl ether, of a polyhydric organic compoundselected from the class consisting of a polyhydric alcohol and phenolshaving at least two phenol hydroxy groups, and (3) about 4 to 40 partsby weight of hexachloroendomethylenetetrahydrophthalic anhydride.

2. A composition of matter comprising the reaction product of- (1) about300 to 650 parts by weight of a carboxyl, rich alkyd resin comprisingthe esterification product of from about 0.7 to, 1.5 mols of a materialselected from the class consisting ofhexachloroendomethylenetetrahydrophthalic anhydride andhexachloroendomethylenetetrahydrophthalic acid and about one mol ofmonoglyceride of a fatty acid having at least 13 carbon atoms, saidalkyd resin having an acid number of'from about 25 to 35, (2) aboutparts by weight of a complex epoxide resin containing epoxide groups andcomprising a polyglycidyl ether of a polyhydric organic compoundselected from the class consisting of a polyhydric alcohol and phenolshaving at least two phenol hydroxy groups, and (3) about 4 to 40 partsby weight of hexachloroendomethylenetetrahydrophthalic anhydride.

3. A composition of matter comprising the reaction product of (1) about300 to 650 parts by weight of a carboxyl rich alkyd resin comprising theesterification product of from about 0.7 to 1.5 mols of a materialselected from the class consisting ofhexachloroendomethylenetetrahydrophthalic anhydride andhexachloroendomethylenetetrahydrophthalic acid and about one mol of amonoglyceride of a fatty acid having at least 13 carbon atoms, said.alkyl resin having an acid number of about 30, (2) about 100 parts byweight of a complex epoxide resin containing epoxide groups andcomprising a polyglycidyl ether of a polyhydric organic compoundselected from the class consisting of a polyhydric' alcohol and phenolshaving at least two'phenol hydroxy groups, and (3') about 4 to 40 partsby weight of hexachloroendomethylenetetrahydrophthalic anhydride.

4. A'composition of matter comprising the reaction product of (1) about300 to 650 parts by weight of a carboxyl rich alkyd resin comprising theesterification product of from about 0.7 to 1.5 mols of a materialselected from the class consisting ofhexachloroendomethylenetetrahydrophthalic anhydride andhexachloroendomethylenetetrahydrophthalic acid and about one mol ofglyceryl monoricinoleate and having an acid number of from about 18 to35, (2) about 100 parts by weight of a complex epoxide resin containingepoxide groups and comprising a polyglycidyl ether of a polyhydricorganic compound selected from the class consisting of a polyhydricalcohol and phenols having at least two phenol hydroxy groups, and (3)about 4 to 40 parts by weight ofhexachloroendomethylenetetrahydrophthalic anhydride.

5. A composition of matter comprising the reaction product of (1) about300 to 650 parts by weight of a carboxyl rich alkyd resin comprising theesterification product of from about 0.7 to 1.5 mols of a materialselected from the class consisting ofhexachloroendomethylenetetrahydrophthalic anhydride andhexachloroendomethylenetetrahydrophthalic acid and about one mol ofhydrogenated glyceryl monoricinoleate and having an acid number of fromabout 18 to 35, (2) about 100 parts by weight of a complex epoxide resincontaining epoxide groups and comprising a polyglycidyl ether of apolyhydric organic compound selected from the class consisting of apolyhydric alcohol and phenols having at least two phenol hydroxygroups, and (3) about 4 to 40 parts by weight ofhexachloroendomethylenetetrahydrophthalic anhydride. I

6. A composition of matter comprising the reaction product of (1) fromabout 300 to 650 parts by weight of a carboxyl rich alkyd resincomprising the reaction product of from about 0.7 to 1.5 mols of amaterial selected from the class consisting ofhexachloroendomethylenetetrahydrophthalic anhydride andhexachloroendomethylenetetrahydrophthalic acid and about one mol of amonoglyceride of stearic acid and having an acid number of from about 18to 35, (2) about 100 parts by weight of a complex epoxide resincontaining epoxide groups and comprising a polyglycidyl ether of apolyhydric organic compound selected from the class consisting of apolyhydric alcohol and phenols having at least two hydroxy groups, and(3) about 4 to 40 parts by weight ofhexachloroendomethylenetetrahydrophthalic anhydride.

. 7. A composition of matter comprising the reaction product of (1)about 300 to 650 parts by weight of a carboxyl rich alkyd resincomprising the esterification product of from about 0.7 to 1.5 mols of amaterial selected from the class consisting ofhexachloroendomethylenetetrahydrophthalic anhydride andhexachloroendomethylenetetrahydrophthalic acid and about one mol of themonoglyceride of oleic .acid and having an acid number of from about 18to 3 5, (2) about 100 parts by weight of a complex epoxide resincontaining epoxide groups and comprising a polyglycidyl ether of apolyhydric organic compound selected from the class consisting of apolyhydric alcohol and phenols having at least two phenol hydroxygroups, and (3) hexachloroendomethylenetetrahydrophthalic anhydride.

8. A composition of matter comprising the reaction product of (1) about300 to 650 parts by weight of a carboxyl rich alkyd resin comprising theesterification product of from about 0.7 to 1.5 mols of materialselected from the class consisting ofhexachloroendomethylenetetrahydrophthalic anhydride andhexachloroendomethylenetetrahydrophthalic acid and about one mol ofmonoglyceride of palmitic acid and having an acid number of from about18 to 35, (2) about 100 parts by weight of a complex epoxide resincontaining epoxide groups and comprising a polyglycidyl ether of apolyhydric organic compound selected from the class consisting ofa-polyhydric alcohol and phenols having at least two phenol hydroxygroups, and (3) about 4 to 40 parts by weight ofhexachloroendomethylenetetrahydrophthalic anhydride.

9. The process of preparing a heat and flame resistant, flexibleresinous composition which comprises (1) mixing about 300 to 650 partsby weight of a carboxyl rich alkyd resin, said alkyd resin being theesterification product of from about 0.7 to 1.5 mols of a materialselected from the class consisting ofhexachloroendomethylenetetrahydrophthalic anhydride andhexachloroendomethylenetetrahydrophthalic acid and about one mol of amonoglyceride of a fatty acid having at least 13 carbon atoms, withabout parts by weight of a complex epoxide resin containing epoxidegroups and comprising a polyglycidyl ether of a polyhydric organiccompound selected from the class consisting of polyhydric alcohol andphenols having at least two phenol hydroxy groups, and (2) adding tosaid mixture about 4 to 40 parts by Weight ofhexachloroendomethylenetetrahydrophthalic anhydride, and (3) curing withheat at an elevated temperature.

10. The process of preparing a heat and flame resistant flexibleresinous composition which comprises (1) mixing and heating at atemperature of the order of C. to C. about 300 to 650 parts by weight ofa carboxyl rich alkyd resin, said alkyd resin being the esterificationproduct of from about 0.7 to 1.5 mols of a material selected from theclass consisting of hexachloroendomethylenetetrahydrophthalic anhydrideand hexachloroendomethylenetetrahydrophthalic acid and about one mol ofa monoglyceride of a fatty acid having at least 13 carbon atoms, withabout 100 parts by weight of a complex epoxide resin containing epoxidegroups and comprising a polyglycidyl ether of a polyhydric organiccompound selected from the class consisting of a polyhydric alcohol andphenols having at least two phenol hydroxy groups, and (2) adding tosaid mixture about 4 to 40 parts by weight ofhexachloroendomethylenetetrahydrophthalic anhydride and (3) curing withheat at an elevated temperature.

References Cited in the file of this patent UNITED STATES PATENTS DoyleOct. 15, 1954 l l g UNITED STATES PATENT OFFICE QERTIFICATE OFCORRECTION Patent N00 2,969,495 October 1959 Joseph Rosenberg It isherebjr certified that error appears in the -printed specification ofthe above numbered patent requiring correction and that the said LettersPatent should read as corrected below.

Column 6, line 13, after moi of" insert column '7, line 26, after "(3)"insert about A, to 40 parts by We ght of Signed and sealed this 19th dayof April 1969.,

(SEAL) Attest:

KARL H. AXLINE ROBERT c. WATSON Attesting Officer Commissioner ofPatents

1. A COMPOSITION OF MATTER COMPRISING THE REACTION PRODUCT OF (1) ABOUT 300 TO 650 PARTS BY WEIGHT OF A CARBOXYL RICH ALKYD RESIN COMPRISING THE ESTERFICATION PRODUCT OF ROM ABOUT 0.7 TO 1.5 MOLS OF A MATERIAL SELECTED FROM THE CLASS CONSISTING OF HEXACHLOROENDOMETHYLENETETRAHYDROPHTHALIC ANHYDRIDE AND HEXACHLOROENDOMETHYLENETETRAHYDROPHTHALIC ACID AND ABOUT ONE MOL OF A MONOGLYCERIDE OF A FATTY ACID HAVING AT LEAST 13 CARBON ATOMS, SAID ALKYD RESIN HAVING AN ACID NUMBER OF FROM ABOUT 18 TO 35,(2) ABOUT 100 PARTS BY WEIGHT OF A COMPLEX EPOXIDE RESIN CONTAINING EPOXIDE GROUPS AND COMPRISING A POLYGLYCIDYL ETHER OF A POLYHYDRIC ORGANIC COMPOUND SELECTED FRO THE CLASS CONSISTING OF A POLYHYDRIC ALCOHOL AND PHENOLS HAVING AT LEAST TWO PHENOL HYDROXY GROUPS, AND (3) ABOUT 4 TO 40 PARTS BY WEIGHT OF HEXACHLOROENDOMETHYLENETETRAHYDROPHTHALIC ANYDRIDE. 